WO2019203280A1

WO2019203280A1 - Insecticidal multifilament and woven or knitted article

Info

Publication number: WO2019203280A1
Application number: PCT/JP2019/016529
Authority: WO
Inventors: ▲たかし▼ 印藤; 剛人内田; 直也勝山; 浩義中田; はるな星島; 貴也平野; 高橋　徹
Original assignee: ダイオ化成株式会社
Priority date: 2018-04-17
Filing date: 2019-04-17
Publication date: 2019-10-24
Also published as: JP7136579B2; JP2019183352A

Abstract

The purpose of the present invention is to provide: an insecticidal multifilament with which it is possible to achieve maximum insecticidal properties over a long period of time, and furthermore to avoid thread breakage and maintain good quality; a method for manufacturing the insecticidal multifilament; and a woven or knitted article using the insecticidal multifilament. The present invention provides an insecticidal dyed multifilament in which Etofenprox is contained in a matrix resin, wherein the insecticidal multifilament is characterized in that when dyed, the Etofenprox is contained in a proportion of 0.18-1.35 mass%, and when not dyed, the Etofenprox is contained in a proportion of 0.30-2.25 mass%, and also provided are a method for manufacturing the insecticidal multifilament, and a woven or knitted article using the insecticidal multifilament.

Description

Insect-proof multifilament and knitted fabric

The present invention relates to an insect-proof multifilament and a woven or knitted fabric. More specifically, the insect-proof multifilament containing etofenprox in a low-melting copolymer polyethylene terephthalate resin or polytrimethylene terephthalate resin, and the multifilament It relates to the woven or knitted fabric used.

In recent years, attempts have been made to impart insect repellent properties to various fabric products and insect nets such as screen doors by using an insect repellent.

For example, Patent Document 1 discloses an insect repellent net in which an insect repellent is contained in a multifilament yarn race. The insect net of Patent Document 1 is manufactured by impregnating a multifilament yarn lace with an aqueous liquid containing an insect repellent and an adhesive and then drying. The insect net of Patent Document 1 not only physically prevents insects from entering the indoor space, but also exhibits chemical insect repellent properties using insect repellents. Furthermore, since the insect repellent is fixed to the gaps of many filaments and the knots of the lace, the amount of the insect repellent is large and the insect repellent is difficult to fall off. However, even with the insect net of Patent Document 1, the insect repellent falls off when a strong stress such as friction is applied. Furthermore, even if the insect repellent can be held on the race surface for a long time without dropping off, the insect repellent gradually loses its effect over time. Thus, the insect net of Patent Document 1 still has room for improvement in terms of sustaining insect repellent properties.

Patent Document 2 discloses an insect repellent monofilament comprising a resin composition containing 1 to 15 parts by weight of a pest repellent with respect to 100 parts by weight of a thermoplastic resin, and a fabric using such an insect repellent monofilament. Yes.

JP 2001-220970 A JP 2008-169141 A

However, as a result of intensive studies by the inventor, even though etofenprox, which is an insect repellent, can be used without any problem as long as it is a monofilament that is a single thick yarn as in Patent Document 2, a multi-layer composed of a plurality of thin filaments is used. It was found that when used as a filament, the insect repellent could not be fully exhibited. Alternatively, it is conceivable to use a large amount of etofenprox in order to give sufficient insect repellent properties, but if the amount of etofenprox used is excessive, yarn breakage or yarn fluff is likely to occur, and spinning operability It was also found that was damaged.

Accordingly, an object of the present invention is to provide an insect repellent multifilament capable of maximizing insect repellent over a long period of time and maintaining good quality by avoiding yarn breakage and the like, and a method for producing the same. It is to be.

In addition, another object of the present invention is to provide an insect-proof woven fabric or knitted fabric capable of maximizing insect-proofing properties over a long period of time.

According to the present invention, in the insect-repellent dyeing multifilament in which etofenprox is contained and dyed in the matrix resin, is the matrix resin a copolymerized polyethylene terephthalate resin having a melting point of 210 to 250 ° C. Or a polytrimethylene terephthalate resin, wherein the etofenprox content is 0.18 to 1.35% by mass. The matrix resin is preferably the copolymerized polyethylene terephthalate resin.
Furthermore, according to the present invention, an insect-proof fabric or knitted fabric using such insect-proof dyed multifilaments is provided. The insect-repellent dyeing multifilament preferably has a fineness of 30 to 2000 dtex and a number of single yarns of 10 to 300.

In addition, according to the present invention, in the matrix resin, etofenprox is contained, and in the insect-proof undyed multifilament that is not dyed, the matrix resin is a copolymer polyethylene terephthalate resin having a melting point of 210 to 250 ° C. Or a polytrimethylene terephthalate resin, and the content of etofenprox is 0.30 to 2.25% by mass. The matrix resin is preferably the copolymerized polyethylene terephthalate resin.
Furthermore, according to the present invention, there is provided an insect-proof fabric or knitted fabric using such insect-proof undyed multifilament. The insect-proof undyed multifilament preferably has a fineness of 30 to 2000 dtex and a number of single yarns of 10 to 300.

According to the present invention, a copolymer polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or polytrimethylene terephthalate resin is prepared as a matrix resin, and 0.4 to 5.00 mass of etofenprox in the matrix resin. % To obtain a mixture. The mixture is melt-kneaded at a temperature of the melting point of the matrix resin + 10 to 40 ° C., and the resulting melt-kneaded material is spun and dyed to obtain etofenprox in an amount of 0.00. There is provided a method for producing an insect-repellent dyed multifilament characterized by obtaining an insect-repellent dyed multi-filament containing 18 to 1.35% by mass. The matrix resin is preferably the copolymerized polyethylene terephthalate.

According to the present invention, a copolymer polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or polytrimethylene terephthalate resin is prepared as the matrix resin, and etofenprox is added to the matrix resin in an amount of 0.40 to 5. 00% by mass is mixed to obtain a mixture. The mixture is melt-kneaded at a temperature of the melting point of the matrix resin + 10 to 40 ° C., and the obtained melt-kneaded product is spun to obtain etofenprox of 0.30. There is provided a method for producing an insect-repellent undyed multifilament characterized by obtaining an insect-repellent undyed multifilament contained in an amount of ˜2.25% by mass. The matrix resin is preferably the copolymerized polyethylene terephthalate resin.

In the present specification, the insect-proof dyed multifilament and the insect-proof unstained multi-filament are sometimes collectively referred to as insect-proof multifilament. Similarly, the woven fabric or knitted fabric using the insect-proof dyed multifilament and the woven fabric or knitted fabric using the insect-proof undyed multifilament may be collectively referred to as a woven or knitted fabric.

In the insect-proof multifilament and insect-proof woven or knitted fabric of the present invention, etofenprox is kneaded into the multifilament, and when insects such as mosquitoes touch the etofenprox on the surface of the multifilament, they hate it and leave. Insect protection is demonstrated by the principle. In the present invention, etofenprox gradually exudes from the inside of the multifilament over time, so that the insect repellent can be exhibited over a long period of time.

Although a technique for kneading etofenprox into a filament has existed for a while (for example, Patent Document 2), such a technique is only related to a monofilament and could not provide sufficient insecticidal properties to a multifilament. However, the present invention succeeds in making the used etofenprox exhibit maximum insect repellent properties in a multifilament. The reason is not clear, but the present inventor thinks as follows.

That is, the insect repellent filament is obtained by blending materials such as a matrix resin and an insect repellent, and heating the blend to a temperature higher than the melting point of the resin to perform melt spinning. When etofenprox is used as an insect repellent, 2- (4-ethoxyphenyl) has a low melting point and is easily sublimated, so if it is exposed to an excessively high temperature, it often volatilizes out of the filament. .

Particularly, the present invention relates to a multifilament composed of a plurality of thin threads, not a monofilament which is a single thick thread. Multifilaments have a larger surface area than monofilaments and are therefore particularly prone to volatilization due to the excessively high temperatures described above.

However, in the present invention, a low melting point (210 to 250 ° C.) copolymer polyethylene terephthalate resin (hereinafter sometimes abbreviated as copolymer PET resin) or polytrimethylene terephthalate resin (hereinafter PTT) is used as the matrix resin. Abbreviated as resin). PTT resin is a low melting point resin having a melting point of only about 230 ° C. even in a homopolymer state. Thus, by using a low melting point matrix resin, the melting temperature during spinning can be lowered, and volatilization of etofenprox can be effectively suppressed. As a result, in the present invention, a sufficient amount of etofenprox can be present in the multifilament without using a large amount of etofenprox as a material. It is considered that the insect repellent can be exhibited to the maximum and for a long time.

Furthermore, in the present invention, by using the above-described low melting point matrix resin, volatilization of etofenprox in the dyeing process is also suppressed. In detail, for example, after processing a multifilament after spinning into a woven or knitted fabric, a dyeing bath in which a dye or the like is dissolved is heated to a predetermined temperature, and dyeing is performed by immersing the woven or knitted fabric in the dyeing bath for several hours. There is. So far, it has not been thought that a large amount of etofenprox is lost in the dyeing process, but the present inventors have found that the loss of etofenprox occurs more in the dyeing process than in the melt spinning process. . This is a surprising fact considering that the dyeing temperature is lower than the melting temperature at the time of spinning. The inventor presumes that in the dyeing process, the amount of loss increases as a result of the multifilament being heated for a long time. However, in the present invention, since the low melting point matrix resin is employed as described above, the dyeing temperature can be suppressed, and even if the immersion time is long, etofenprox is hardly lost.

In this way, in the present invention, the loss of etofenprox in the spinning process, which is essential for producing multifilaments, by a very simple means of adopting a low melting point copolymerized PET resin or PTT resin as a matrix resin. In addition, the amount of etofenprox can be maintained even in a dyeing process in which a large amount of etofenprox is lost. Therefore, since it is not necessary to mix | blend excess etofenprox, it has succeeded in the implementation | achievement of the multifilament which exhibits high insect-proofing property, avoiding thread breakage etc. and maintaining favorable quality.

Further, the copolymerized PET resin and PTT resin are resins having excellent heat shrinkage resistance and dyeing fastness. By using these resins, we have succeeded in realizing a multifilament which is excellent in heat shrinkage resistance or dyeing fastness and exhibits high insect repellent properties.

In addition, there are polyethylene terephthalate homopolymers (PET homopolymers) as other resins excellent in heat shrinkage resistance and dyeing fastness, but PET homopolymer has a high melting point of 265 ° C., and the amount of etofenprox loss during production. In order to increase the amount, excess etofenprox must be added. In that respect, since the matrix resin used in the present invention has a low melting point, it is possible to avoid such inconveniences and to obtain heat shrinkage resistance and dyeing fastness.

The present invention relates to an insect-proof multifilament and an insect-proof woven or knitted fabric using the multi-filament.

<Insect repellent multifilament>
In the insect repellent multifilament of the present invention, etofenprox which is an insect repellent is kneaded into a matrix resin. As the matrix resin, any one of a copolymerized PET resin and a PTT resin can be used, and a mixture of a copolymerized PET resin and a PTT resin can also be used under the condition that the effect of the present invention is not impaired. .

The copolymerized PET resin has a structure in which terephthalic acid that is a carboxylic acid unit and ethylene glycol that is an alcohol unit are ester-bonded, and further includes at least one dicarboxylic acid other than terephthalic acid as a carboxylic acid unit, or It is a polyester resin containing at least one alcohol other than ethylene glycol as an alcohol unit. Of course, both dicarboxylic acids other than terephthalic acid and alcohols other than ethylene glycol may be included.

The ratio of the dicarboxylic acid other than terephthalic acid and the alcohol other than ethylene glycol is 1 mol% or more and less than 50 mol%, preferably 1 mol% or more and less than 30 mol% in all segments of the copolymerized PET resin.

From the viewpoint of spinning operability, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably 50 mol% or more, more preferably 70 mol% or more. Similarly, the proportion of ethylene glycol in the alcohol unit is preferably It is 50 mol% or more, more preferably 70 mol% or more.

Examples of dicarboxylic acids other than terephthalic acid that may be contained in the copolymerized PET resin include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Biphenyl-2,2′-dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, bis (4,4′-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4 Aromatic dicarboxylic acids such as' -diphenyl ether dicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid; and adipic acid, sebacic acid, azelaic acid, dimer Aliphatic dicarboxylic acids such as acids; and the like.

Examples of the alcohol unit other than ethylene glycol that may be contained in the copolymerized PET resin include aliphatic or alicyclic diols having 2 to 20 carbon atoms, bisphenol derivatives, and the like. Specifically, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexane dimethanol, 4,4′-dicyclohexyl Examples thereof include hydroxymethane, 4,4′-dicyclohexylhydroxypropane, bisphenol A ethylene oxide addition diol, and the like.

In addition to the above-mentioned bifunctional monomers, trifunctional or higher polyfunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, triol (for example, glycerin, trimethylolpropane) and molecular weight are introduced to introduce a branched structure. A small amount of a monofunctional compound such as a fatty acid can also be used for adjustment.

The intrinsic viscosity (IV) of the copolymerized PET resin used in the present invention is preferably 0.5 to 1.0 dl / g. The intrinsic viscosity can be measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

It is important that the copolymerized PET resin used in the present invention has a melting point of 210 to 250 ° C., preferably 220 to 240 ° C. If the melting point is too high, the melting temperature in the spinning process and the dyeing temperature in the dyeing process must be increased, and a lot of etofenprox will be volatilized in these processes, and if the melting point is too low, the heat resistance will be increased. This is because the above becomes insufficient. The melting point can be confirmed, for example, by differential scanning calorimetry. In order to obtain a PET resin having such a melting point, a known means may be taken as necessary. For example, an appropriate type and an appropriate amount of a copolymer component may be blended to adjust the melting point.

In the present invention, the type and ratio of copolymerized units are appropriately selected so that copolymerized PET having such a melting point can be obtained. Preferred copolymerized PET resins include polyester ether resins copolymerized with polyalkylene glycols, particularly polytetramethylene glycol, dimer acid copolymerized PET resins, and isophthalic acid copolymerized PET resins.

Copolymerized PET resin is excellent in heat shrinkage resistance, dyeing fastness and washing shrinkage resistance, and is suitable for various applications.

The PTT resin is a polyester resin having a structure in which a terephthalic acid unit and a trimethylene glycol unit are ester-bonded, and in addition to a PTT homopolymer, a PTT copolymer containing a copolymer unit other than a terephthalic acid unit or a trimethylene glycol unit. Polymers and mixtures of PTT homopolymers and PTT copolymers are included.

Examples of the dicarboxylic acid other than terephthalic acid that may be contained in the copolymerized PTT resin include the same examples as the dicarboxylic acid other than terephthalic acid that may be contained in the copolymerized PET resin.

Examples of the alcohol unit other than trimethylene glycol that may be contained in the copolymerized PTT resin include the same examples as the alcohol unit other than ethylene glycol and ethylene glycol that may be contained in the copolymerized PET resin.

In the copolymerized PTT resin, a small amount of a polyfunctional monomer for introducing a branched structure and a monofunctional compound for adjusting the molecular weight can be used in combination with the copolymerized PET resin.

The intrinsic viscosity (IV) of the PTT resin used in the present invention is preferably 0.6 to 1.0 dl / g.

PTT resin has a low melting point of about 230 ° C in a homopolymer state, excellent dyeing fastness and texture, and low-temperature dyeing properties derived from low crystallinity brought about by the zigzag structure of the molecular chain. Therefore, it is a useful resin, but it may be a copolymer for the purpose of further reducing the melting point or adjusting the texture. Preferable copolymers include polyester ether resins copolymerized with polyalkylene glycols, particularly polytetramethylene glycol, dimer acid copolymerized PTT resins, and isophthalic acid copolymerized PTT resins. The copolymer means a copolymer having an amount of copolymerization of 1 mol% or more and less than 50 mol%, preferably 1 mol% or more and less than 30 mol% in all segments of the PTT resin.

In the case of a copolymer, it is preferable to select the type and ratio of the copolymer unit so that the melting point is 210 to 240 ° C. from the viewpoint of the balance between heat resistance and the suppression of volatilization of etofenprox.

As the matrix resin, a copolymerized PET resin is preferable because it is easily available and highly versatile.
Moreover, it is preferable that content of matrix resin is 70 mass% or more with respect to the whole multifilament.

Etofenprox has the chemical name 2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl ether and exhibits insect repellent by the same mechanism of action as pyrethroid, but is toxic to mixed-blooded animals. It has the advantages of low irritation to skin and mucous membranes and low fish toxicity.

In the insect-proof multifilament of the present invention, when not dyed, etofenprox is contained in an amount of 0.30 to 2.25% by mass, preferably 0.33 to 2.00% by mass. Particularly preferably, the content is 0.56 to 2.00% by mass. That is, in the present invention, since the matrix resin has a low melting point, the heating temperature at the time of spinning can be lowered. Therefore, it effectively suppresses the evaporation of etofenprox during spinning, is susceptible to temperature, and contains a sufficient amount of etofenprox even though it is a multifilament that requires delicate spinning conditions. And exhibits good insect repellent properties. If the content ratio of etofenprox exceeds the above numerical range, the spinning operability, stretching operability, and weaving / knitting processability may be impaired. In addition, the texture may be impaired.

The insect-repellent dyed multifilament obtained by dyeing the above-mentioned insect-repellent undyed multifilament contains 0.18 to 1.35% by mass of etofenprox, preferably 0.20 to 1.30. % By weight, particularly preferably 0.22 to 1.20% by weight, and most preferably 0.34 to 1.20% by weight. By using a low melting point matrix resin, not only the heating temperature at the time of spinning described above, but also when dyeing, the dyeing temperature can be lowered. Contains sufficient amounts of etofenprox, even after staining. When the content ratio of etofenprox exceeds the above numerical range, the spinning operability, stretching operability, weaving / knitting workability, and texture may be impaired as in the case of not dyeing. Furthermore, when the content ratio of etofenprox exceeds the above numerical range, the dyeing color tone may be lightly dyed (lighter color).

In addition, when the multifilament has not been dyed, it means that the multifilament has not been dyed, and as long as it has not been dyed, it includes multifilaments deposited with pigments such as inorganic pigments and organic pigments. On the other hand, when the multifilament is dyed, it includes those dyed after processing into woven and knitted fabrics, and those dyed before processing, and also dyes multifilaments deposited with pigments. Also included.

In the present invention, a known insect repellent may be used in combination with etofenprox as long as the effect is not impaired. Examples of known insect repellents other than etofenprox include pyrethroid insecticides such as pyrethrin, cinerine, jasmolin, allethrin, resmethrin, and fenvalerate; cyclic diene insect repellents such as toxaphene and benzoepin; And phosphorus insect repellents; carbamate insect repellents such as carbaryl, mesomil and promecarb;

The multifilament of the present invention may further contain a known additive. Known additives include, for example, sustained release aids such as benzenesulfonic acid amide; dissimilar thermoplastic resins used as dispersion aid resins, affinity resins (eg, ethylene-ethyl acrylate); weathering agents; Flame retardants; antioxidants; inorganic pigments such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, silicon carbide, barium sulfate, and carbon black; organic pigments such as phthalocyanine metal-based and cobalt blue; metal stearates; ethylene bis Stearylamide; calcium metasilicate; hydrous magnesium silicate; aminosilane; melamine cyanurate; ionomers; sequestering agent; clathrate compound; Epoxy compound; Oxazoline compound; Clay, Talc Kaolin, particles such as inorganic particles or crosslinked polymer particles such as zirconium acid; antioxidants; ion exchanger; and the like.
An embodiment in which a pigment such as an inorganic pigment or an organic pigment is used as an additive and the dyeing step is omitted is preferable in that a multifilament exhibiting a desired color can be obtained while suppressing the volatilization of etofenprox. .

In the present invention, the equivalent circle diameter of the cross section of the single yarn constituting the multifilament can be set as appropriate, but is usually preferably less than 50 μm and more preferably less than 45 μm.

The fineness of the multifilament of the present invention may be appropriately determined according to the application, but generally 30 to 2000 dtex is preferable, and 30 to 300 dtex is more preferable. If the multifilament is too thin, thread breakage or single thread breakage (yarn fluff) may occur easily. If the multifilament is too thick, desired quality (flexibility, texture) may not be obtained.

The number of single filaments of the multifilament of the present invention may be appropriately determined according to the use, but is preferably 10 to 300, more preferably 12 to 48, and more preferably 12 to 36 from the viewpoint of spinning ease and cost. Particularly preferred.

The multifilament of the present invention can be produced by a known method. For example, a desired material is prepared, and the material is melt-kneaded at a temperature as low as possible by a conventional melt spinning apparatus, preferably at a melting point of the matrix resin +10 to 40 ° C., particularly +10 to 30 ° C.

各 Each material may be mixed directly, but if necessary, it may be mixed after making it into a master batch. A known thermoplastic resin may be used for the master batch.

¡Matrix resin needs to be dried before melting after mixing the materials to spin off the moisture before spinning. The drying conditions are preferably 80 to 130 ° C. for 3 to 6 hours.

The blending amount of the material may be appropriately determined so that the amount of each component in the finally obtained multifilament falls within the above numerical range. For example, the matrix resin is preferably used in an amount of 73 to 95% by mass with respect to the entire material. Further, etofenprox (pure) is preferably used in an amount of 0.40 to 5.00% by mass, more preferably 0.45 to 4.00% by mass, based on the whole material, and 0.60. It is particularly preferable to use ˜3.50% by mass, and it is most preferable to use 1.12 to 3.50% by mass. At this time, it is preferable that etofenprox is uniformly dispersed in the melt-kneaded product without a concentration gradient.

Next, the melt-kneaded product is extruded. When extruding, it is important to shorten the residence time to avoid excessive heat history. Although depending on the scale of the apparatus and the like, the residence time is usually preferably 2 to 10 minutes, particularly preferably 4 to 8 minutes. If the residence time is too short, melt and kneading may be insufficient, resulting in yarn, and yarn breakage may occur easily. If the residence time is too long, it causes an increase in the amount of etofenprox volatilized during spinning, which is not preferable. Moreover, there is a possibility that inconveniences such as a decrease in viscosity, yellowing, and insufficient strength elongation may occur.

Next, the extruded melt-kneaded material is discharged from the die, and air is blown to cool and solidify. Thereby, an undrawn yarn is obtained. It is preferable that etofenprox is uniformly dispersed in the undrawn yarn without a concentration gradient.

Next, the obtained undrawn yarn is drawn. The stretching temperature is preferably 30 to 80 ° C. The draw ratio is preferably 3.0 to 5.5 times.

Next, if necessary, the multifilament before being used for weaving or knitting may be dyed. That is, usually, dyeing is often performed after weaving or knitting, but depending on the application or the like, it may be performed before weaving or the like. For dyeing, for example, a dyeing bath in which a known dye and an auxiliary agent are dissolved is prepared, and the temperature is adjusted to 100 to 140 ° C., preferably 100 to 125 ° C. Soak.

The multifilament of the present invention thus obtained contains a sufficient amount of etofenprox not only before dyeing but also after dyeing, and exhibits excellent insect repellent properties. Furthermore, etofenprox is not applied to the surface, but at least immediately after production, it is uniformly kneaded inside the multifilament and oozes out to the surface of the multifilament little by little. Is sustained for a long time. Moreover, the present invention is a multifilament composed of a plurality of thin threads. Multifilaments are generally more susceptible to yarn breakage and yarn fluff than monofilaments. In particular, when a foreign substance such as etofenprox is kneaded into the resin, the problems of spinning operability such as yarn breakage and yarn fluff are very remarkable. However, in the present invention, by using a low melting point PBT, avoiding the use of a large amount of etofenprox, and preferably by finely adjusting the spinning conditions, the occurrence of yarn breakage and yarn fluff can be effectively suppressed. Yes.

The insect-proof multifilament of the present invention may be used as it is in the state of a long fiber, but may be cut into an appropriate length and used in the state of a short fiber.
As a case where it is used in the state of short fibers, it can be considered that it is used for, for example, a woven fabric, a knitted fabric, a nonwoven fabric, and various auxiliary materials. In use, short fibers may be twisted and used as a spun yarn.
Examples of the use as long fibers include use as yarns and use in woven or knitted fabrics.
From the viewpoint that the effects of the present invention can be maximized, it is preferable to use the insect-proof multifilament of the present invention in a woven fabric or a knitted fabric while maintaining the long fibers.

<Weaving and knitting>
In the present invention, the insect-proof multifilament of the present invention as a long fiber is used as at least part of warp or weft, preferably as all warp or all weft, particularly preferably all warp and all warp. It can be used as a weft to obtain a woven fabric. Hereinafter, such a woven fabric may be referred to as the woven fabric of the present invention.

A known fabric structure can be applied to the fabric of the present invention. Examples of the woven fabric structure include, for example, a Mihara organization (plain weave, oblique weave, satin weaving, etc.), change organization (variation plain weave, satin weaving, change oblique weaving, sudden oblique, Yamagata oblique, altered satin weaving, etc.) Single organization such as special tissue (Hachisu or pear fabric), mixed tissue, etc .; double weaving (such as ball rasha), vertical double weaving (double-sided satin, etc.), double organization (such as Futsuori, bag weaving), etc. Examples include a pile structure (vertical velvet, etc.), a pile structure (bendaku, corduroy, etc.) and a pile structure such as a towel structure; In addition to the specific examples described above, there is a fabric structure described in JIS L 0206: 1999.

Weaving may be performed according to a known method, that is, a known method may be selected according to the selected fabric structure or the like.

Further, in the present invention, the insect-proof multifilament of the present invention as a long fiber is used as at least a part of the knitting yarn, preferably as all the knitting yarns, and warp knitting or weft knitting to obtain a knitted fabric You can also. Hereinafter, such a knitted fabric may be referred to as a knitted fabric of the present invention, and may be collectively referred to as a woven or knitted fabric of the present invention together with the above-described woven fabric of the present invention.

A well-known knitting structure can be applied to the knitted fabric of the present invention. Examples of the knitting structure include weft knitting structures such as flat knitting, rib knitting, pearl knitting, and double-side knitting; warp knitting structures such as single denby knitting, single cord knitting, single atlas knitting, and half tricot knitting. Depending on the knitting structure, pattern yarn may be used in addition to the knitting yarn (ground yarn). As the handle yarn, the multifilament of the present invention may be used, or a known yarn may be used.

The knitting may be performed according to a known method, that is, an appropriate known method may be selected according to the selected knitting structure or the like.

Prior to weaving the woven fabric of the present invention or knitting the knitted fabric of the present invention, the multifilament of the present invention described above may be wound, and preparations such as warping and gluing may be made.

After weaving or knitting, the woven or knitted fabric obtained may be dyed depending on the intended use. Dyeing may be performed by a known dip dyeing or printing method. Due to the fact that the multifilament matrix resin is a low melting copolymer PET resin or PTT resin, the present invention can lower the heating temperature of each step including the dyeing temperature, It has an important feature in that it effectively suppresses the volatilization of Fenprox. For example, in the case of dip dyeing, if necessary, the knitted or knitted fabric is heated as a preset at 120 to 160 ° C. at a speed of 15 to 30 m / min. Next, a dyeing bath in which a known dye and an auxiliary agent are dissolved is prepared, and the temperature is adjusted to 100 to 140 ° C., preferably 100 to 125 ° C. The woven or knitted fabric is soaked in this bathtub and dyed. During the immersion, the inside of the bathtub is preferably stirred. After dyeing, if necessary, the knitted or knitted fabric may be heated as a final set at 130 to 170 ° C. at a speed of 15 to 25 m / min. If the woven or knitted fabric is exposed to an excessively high temperature in this dyeing process or is heated for an excessively long time, etofenprox present in a sufficient amount in the multifilament may be volatilized in the dyeing process. Therefore, it is preferable to set the heating temperature and the heating time in each heating operation in the dyeing process within the above-described numerical ranges to avoid a decrease in etofenprox in the dyeing process.

After weaving and knitting, or after dyeing as necessary, the woven or knitted fabric is subjected to finish processing such as texture adjustment using a softener or glue, and correction of fabric distortion by heating at a temperature of 120 to 160 ° C. It's okay.

In the woven or knitted fabric of the present invention thus obtained, if not dyed, etofenprox is 0.30 to 2.25% by mass, preferably 0.33 to 2.00% by mass in the insect-proof undyed multifilament, The amount is particularly preferably 0.56 to 2.00% by mass.
On the other hand, when dyed, in the woven or knitted fabric of the present invention, etofenprox is 0.18 to 1.35% by mass, preferably 0.20 to 1.30% by mass, more preferably in the insect-proof dyeing multifilament. It is contained in an amount of 0.22 to 1.20% by mass, most preferably 0.34 to 1.20% by mass.
That is, when the multifilament of the present invention after spinning is used for a woven or knitted fabric, etofenprox may be slightly volatilized by heating in processes such as weaving, knitting, and dyeing. It is preferable that Prox is contained in the multifilament in the woven or knitted fabric in the above-described numerical range.
In addition, etofenprox is 0.12 to 0.88 g / m ² , particularly 0.16 to 0.78 g / m ^{2 in} the entire woven or knitted fabric of the present invention regardless of whether or not dyeing is performed and whether or not other filaments are used. Preferably m ^{2 is} present. In the woven or knitted fabric of the present invention, when the amount of etofenprox satisfies these numerical ranges, a woven or knitted fabric with high product value that has excellent insect repellent properties and that suppresses the occurrence of filament cracking, fluff, etc. can get.

In the woven or knitted fabric of the present invention, it is preferable to use a multifilament having a fineness of 30 to 2000 dtex and a single yarn number of 10 to 300. When the texture is important, it is more preferable to use a multifilament having a fineness of 30 to 300 dtex and a single yarn number of 12 to 48. When importance is attached to high strength and high durability, it is more preferable to use a multifilament having a fineness of 300 to 2000 dtex and a single yarn number of 50 to 300. In order to maximize the effects of the present invention, it is particularly preferable to use a multifilament having a fineness of 30 to 300 dtex and a single yarn number of 12 to 48.

The woven or knitted fabric of the present invention can be widely applied to various uses, that is, not only living materials but also industrial materials. Living materials include, for example, health equipment (trampolines, etc.), bedding, interior (curtains, etc.), clothing, decorative items (hats, scarves, gloves, etc.), strollers, insect nets, air conditioner filters, screen door nets, outdoor equipment (tents) , Eaves, etc.). Industrial materials mean, for example, materials for civil engineering, automobiles, housing, electronics, and aircraft industries.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In each example and comparative example, various characteristics were determined according to the following methods.

<Measurement of the amount of etofenprox in multifilament>
60 mg of multifilaments in the undyed knitted fabric or 60 mg of multifilaments in the dyed knitted fabric were immersed in 50 ml of methanol and stirred at 50 ° C. for 20 hours to extract the drug. Next, the extracted liquid was measured by high performance liquid chromatography, and the content of etofenprox was determined.

<Thread breakage, yarn resistance>
The frequency of yarn breakage during spinning and drawing was counted by the number of times per unit time and evaluated according to the following criteria.
○: 0 times / 2 hr Δ; 1 time / 2 hrs x; 2 times or more / 2 hrs

<Tensile strength, tensile elongation>
According to JIS L-1013: 1999-8.5, the tensile strength and tensile elongation of the multifilaments obtained in the respective examples and comparative examples were measured. Specifically, the sample (40 cm) was attached to a tensile tester (AGSJ-1KN manufactured by Shimadzu Corporation) at a holding interval of 200 mm in a strongly pulled state, and the test was performed at a constant speed extension of 200 mm / min. . Read the elongation when the initial load is applied as looseness (mm), pull the sample further, measure the load and elongation (mm) when the sample is cut, and use the following formula to determine the tensile strength (tensile strength) and elongation The rate (tensile elongation) was calculated. The number of tests was 10, and the average value was calculated.
T _b = SD / F ₀
T _b is the tensile strength, SD represents the strength at break, F ₀ represents a positive amount fineness of the sample.
Elongation rate (%) = [(E ₂ −E ₁ ) / (L + E ₁ )] × 100
E ₁ represents a loose (mm), the elongation at _{E 2} is cut (mm), L is distance between grips (mm).

<Insect repellent>
A selective evasion test was conducted in a shelter test using the habit of preferring a dark space where German cockroaches are dark. Details of the test method are shown below.
First, a sample {undyed knitted fabric or dyed knitted fabric obtained in each example and comparative example (5 cm × 5 cm)}, food, and water were placed in a test container. Next, a nesting shelter was installed on each sample. Next, 10 German cockroaches were placed in a test container. The light was then illuminated from above the test container. After leaving it to stand for 10 hours or more, the shelter was removed while taking a video of the entire test container. From the captured video, the number of German cockroaches in each shelter was counted, and the repelling rate was calculated from the following equation.
Repelling rate (%) = {(C ₀ -C) / C ₀ } × 100
C represents the number of insects of the treated area, C ₀ represents the number of the non-treated group insect.
Evaluation was made according to the following criteria.
○; repellent rate 100%
Δ; repelling rate 60% or more and less than 100% ×; repelling rate less than 60%

<Knitting operability>
The number of yarn breaks during knitting was counted and evaluated according to the following criteria.
○: 0 times / 2 hr, Δ: 1 time / 2 hrs, ×: 2 times or more / 2 hrs

<Texture>
The undyed knitted fabric (20 cm × 20 cm) obtained in each Example and Comparative Example was gently grasped with the palm of the dominant hand, and the softness and repulsive force were recognized from the touch and feel, and evaluated according to the following criteria.
○: Soft and repulsive (sharp feeling)
Δ: Slightly hard ×: Hard or too soft

<Dyed color>
The color tone of the dyed knitted fabric obtained in each Example and Comparative Example was evaluated according to the following criteria.
○: Dark dyeing (good) △; Slightly dyed, ×: Light dyeing (lighter color)

<Dyeing fastness>
The dyeing fastness was evaluated according to JIS L 0849: 2013. The test piece fixed on the friction tester type II was reciprocated 1000 times at a speed of 30 reciprocations per minute with a white cotton cloth for friction applied with a load of 2N, and the degree of contamination was examined. The test was performed in a dry state and a wet state, respectively.

<Dimensional change rate>
The dimensional change rate was evaluated in accordance with JIS L 0217: 1995 “103 Methods for Handling Textile Products”. The detergent used was a weak alkaline detergent (attack highly active bio-EX manufactured by Kao Corporation). The drying method was hanging drying.

<Example 1>
Titanium oxide masterbatch (concentration 40% by weight) (RX-4214 manufactured by Nippon Pigment), etofenprox masterbatch (concentration 20% by weight), copolymerized PET resin (Bell Polyester Co., Ltd., 12 mol isophthalic acid) % Containing Belpet IP121B, IV = 0.62, melting point 224 ° C.). 1 part by mass of titanium oxide masterbatch and 6 parts by mass of etofenprox masterbatch were added to 100 parts by mass of copolymerized PET resin, which is a matrix resin, and dry blended. At this time, the pure mass of etofenprox was 1.12% by mass with respect to the entire material. The blend was then dried at 90 ° C. for 5 hours. The dried dry blend was put into a melt spinning apparatus, and the melt-kneaded product was extruded from the die at a temperature of 250 ° C., a residence time of 8 minutes, and an extrusion rate of 0.5 kg / hr · sp to obtain an undrawn yarn. The obtained undrawn yarn was drawn at a draw ratio of 3.6 times and a drawing temperature of 75 ° C. to obtain an insect-proof multifilament having a fineness of 83 dtex and 12 single yarns.

The obtained undyed multifilament was used for a front heel, a middle heel, and a back heel, and an undyed knitted fabric was obtained using a warp knitting machine (KARL MAYER).

The obtained undyed knitted fabric was dyed. Specifically, after performing presetting at 140 ° C. and 18 m / min, a dyed bathtub having the conditions shown in Table 1 below is prepared, and the undyed knitted fabric after presetting is immersed in this bath at 120 ° C. for 4 hours. did. Thereafter, final setting was performed at 160 ° C. and a speed of 18 m / min.

<Example 2>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 9 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox was 1.64% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 3>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 12 parts by mass of etofenprox masterbatch are blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox is 2.12% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 4>
Example 1 with the exception that 1 part by mass of titanium oxide masterbatch and 15 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox was 2.59% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative Example 1>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 30 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox was 4.58% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative Example 2>
Example except that 1 part by mass of titanium oxide masterbatch and 0.6 part by mass of etofenprox masterbatch are blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox is 0.12% by mass In the same manner as in Example 1, insect-proof unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative Example 3>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 2 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox was 0.39% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative example 4>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 3 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of copolymerized PET resin, and the pure content of etofenprox was 0.58% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

Various measurements were performed on the undyed multifilament, undyed knitted fabric and dyed knitted fabric obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results are shown in Table 2 and Table 3.

<Example 5>
In the same manner as in Example 1, an insect-proof unstained multifilament having a fineness of 83 dtex and a single yarn number of 12 was obtained. Subsequently, the insect-proof unstained multifilaments were combined to obtain a thick insect-proof unstained multifilament having a fineness of 166 decix and 24 single yarns. Subsequently, in the same manner as in Example 1, an undyed knitted fabric was obtained from the obtained thick undyed multifilament. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 6>
In the same manner as in Example 2, an insect-proof unstained multifilament having a fineness of 83 dtex and a single yarn number of 12 was obtained. Subsequently, the insect-proof unstained multifilaments were combined to obtain a thick insect-proof unstained multifilament having a fineness of 166 decix and 24 single yarns. Next, an undyed knitted fabric was obtained from the resulting thick undyed multifilament in the same manner as in Example 2. Next, in the same manner as in Example 2, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

Various measurements were performed on the thick undyed multifilament, undyed knitted fabric and dyed knitted fabric obtained in Examples 5 and 6. The results are shown in Tables 4 and 5.

Comparing Table 5 and Table 3 above, Examples 5 and 6 using thick undyed multifilaments had improved tensile strength, and the tensile elongation was suppressed and the yarns were hard to stretch. I understand that. Although not fully expressed in the evaluation criteria of this experiment, improvement of tensile strength and suppression of tensile elongation contribute to improvement of knitting operability and enable knitting under more severe conditions.

<Comparative Example 5>
Copolymerized PBT resin (PBT resin DURANEX 500LP, melting point 170 ° C., IV = 0.7) used in place of copolymerized PET resin, 1 mass of titanium oxide masterbatch per 100 mass parts of PBT resin Part, 3 parts by mass of etofenprox masterbatch, point of pure ethofenprox 0.58% by mass, point of melt kneading spinning 190 ° C, and point of stretching 50 ° C Except that, an insect-proof unstained multifilament was obtained in the same manner as in Example 1. An undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1.

Example 1 except that the temperature at the time of presetting was set to 110 ° C, that the undyed knitted fabric after the presetting was immersed in a dyeing bath at a temperature of 100 ° C, and the temperature of the final set was set to 125 ° C. The obtained undyed knitted fabric was dyed by the above method.

Various measurements were performed on the dyed knitted fabrics obtained in Example 1 and Comparative Example 5. The results are shown in Table 6. In Table 6, “-” represents shrinkage. Both the fastness to dyeing and the rate of dimensional change were better for the knitted fabric using copolymerized PET as the matrix resin.

Claims

In the insect-repellent dyeing multifilament, which contains etofenprox in the matrix resin and is dyed,
The matrix resin is a copolymerized polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or a polytrimethylene terephthalate resin;
An insect-repellent dyeing multifilament, wherein the content of etofenprox is 0.18 to 1.35% by mass.
The insect-repellent dyeing multifilament according to claim 1, wherein the matrix resin is the copolymerized polyethylene terephthalate resin.
In an insect-repellent unstained multifilament that contains etofenprox in the matrix resin and is not dyed,
The matrix resin is a copolymerized polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or a polytrimethylene terephthalate resin;
An insect-repellent undyed multifilament, wherein the content of etofenprox is 0.30 to 2.25% by mass.
The insect-proof undyed multifilament according to claim 3, wherein the matrix resin is the copolymerized polyethylene terephthalate resin.
An insect-repellent fabric or knitted fabric using the insect-repellent dyeing multifilament according to claim 1.
The insect-proof woven fabric or knitted fabric according to claim 5, wherein the fineness of the insect-proof dyeing multifilament is 30 to 2000 dtex and the number of single yarns is 10 to 300.
An insect repellent fabric or knitted fabric using the insect-repellent undyed multifilament according to claim 3.
The insect-proof woven or knitted fabric according to claim 7, wherein the fineness of the insect-proof undyed multifilament is 30 to 2000 decitex and the number of single yarns is 10 to 300.
A copolymer polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or polytrimethylene terephthalate resin is prepared as a matrix resin, and 0.40 to 5.00% by mass of etofenprox is mixed in the matrix resin to obtain a mixture. Get,
The mixture is melt-kneaded at a temperature of the melting point of the matrix resin + 10-40 ° C., and the obtained melt-kneaded material is spun.
Dye
A method for producing an insect-repellent dyeing multifilament, which comprises obtaining an insect-repellent dyeing multifilament containing 0.18 to 1.35% by mass of etofenprox.
The method for producing an insect-repellent dyeing multifilament according to claim 9, wherein the matrix resin is the copolymerized polyethylene terephthalate resin.
As the matrix resin, a copolymerized polyethylene terephthalate resin having a melting point of 210 to 250 ° C. or polytrimethylene terephthalate resin is prepared, and 0.40 to 5.00% by mass of etofenprox is mixed in the matrix resin to obtain a mixture. Get,
The mixture is melt-kneaded at a temperature of the melting point of the matrix resin + 10 to 40 ° C., and the obtained melt-kneaded product is spun.
A method for producing an insect-repellent undyed multifilament, which comprises obtaining an insect-repellent undyed multifilament containing 0.3 to 2.25% by mass of etofenprox.
The method for producing an insect-repellent dyeing multifilament according to claim 11, wherein the matrix resin is the copolymerized polyethylene terephthalate resin.